EP0251636B1 - Feuille composite étirée biaxialement, en résine de styrène - Google Patents

Feuille composite étirée biaxialement, en résine de styrène Download PDF

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Publication number
EP0251636B1
EP0251636B1 EP87305547A EP87305547A EP0251636B1 EP 0251636 B1 EP0251636 B1 EP 0251636B1 EP 87305547 A EP87305547 A EP 87305547A EP 87305547 A EP87305547 A EP 87305547A EP 0251636 B1 EP0251636 B1 EP 0251636B1
Authority
EP
European Patent Office
Prior art keywords
styrene
sheet
polystyrene
biaxially stretched
styrene resin
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP87305547A
Other languages
German (de)
English (en)
Other versions
EP0251636A3 (en
EP0251636A2 (fr
Inventor
Yukihide Tsukamoto
Yasuhiro Sato
Minoru Seino
Akio Toyoda
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
DIC Corp
Original Assignee
Dainippon Ink and Chemicals Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dainippon Ink and Chemicals Co Ltd filed Critical Dainippon Ink and Chemicals Co Ltd
Publication of EP0251636A2 publication Critical patent/EP0251636A2/fr
Publication of EP0251636A3 publication Critical patent/EP0251636A3/en
Application granted granted Critical
Publication of EP0251636B1 publication Critical patent/EP0251636B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/302—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising aromatic vinyl (co)polymers, e.g. styrenic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/03—3 layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/05—5 or more layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/514—Oriented
    • B32B2307/518—Oriented bi-axially
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2439/00—Containers; Receptacles
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S428/00—Stock material or miscellaneous articles
    • Y10S428/91—Product with molecular orientation
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24942—Structurally defined web or sheet [e.g., overall dimension, etc.] including components having same physical characteristic in differing degree
    • Y10T428/2495—Thickness [relative or absolute]
    • Y10T428/24967—Absolute thicknesses specified
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31855—Of addition polymer from unsaturated monomers
    • Y10T428/31909—Next to second addition polymer from unsaturated monomers
    • Y10T428/31924—Including polyene monomers

Definitions

  • This invention relates to a biaxially stretched composite styrene resin sheet of multilayer structure having enhanced tear strength and excellent transparency and being substantially free from the occurrence of cracks or cutting chips during trimming.
  • Biaxially stretched styrene resin sheets have frequently been used in light-weight containers for holding foods because they do not contain substances toxic to humans and have excellent stiffness and moldability. On the other hand, since they are brittle and have low tear strength, they have the defect that when they are trimmed after molding by pressure forming, vacuum forming, etc., cracks and cutting chips occur. In order to remove this defect, a biaxially stretched sheet from a styrene resin softened by addition of high impact polystyrene or a styrene/butadiene block copolymer and having increased tear strength is used.
  • the amount of the high impact polystyrene or styrene/butadiene block copolymer resin is limited because the final sheet will have reduced stiffness and transparency and an increased price. Consequently, the improvement of its strength, particularly tear strength, is not sufficient. Thus, even if the speed of producing molded products from the above sheet by a pressure forming machine or a vacuum forming machine is increased, the number of molded products trimmed cannot be increased. Furthermore, since inspection of cracked products is time-consuming, the molded products are left as a tall pile.
  • a biaxially stretched sheet of a multilayer structure comprising at least two layers of polystyrene and at least three layers of a mixture of polystyrene and styrene/butadiene block copolymer resin, wherein both outside layers are formed of said mixture and the layers of polystyrene and of the styrene resin mixture alternate within the structure, the thickness of each of the outside layers is 1 to 20% of the total thickness of said sheet, and the entire sheet is biaxially stretched.
  • the biaxially stretched composite styrene resin sheet in accordance with this invention includes the following embodiments.
  • Polystyrene used in this invention preferably has a weight average molecular weight of l00,000 to 600,000.
  • the styrene/butadiene block copolymer resin as used in this invention denotes a block copolymer resin composed of units of chains of styrene and units of chains of butadiene. Preferably, it is composed of 20 to 90% by weight of the styrene units and 80 to l0% by weight of the butadiene units and has a melt flow index (JIS K-6870) of 3 to l2 g/l0 min.
  • JIS K-6870 melt flow index
  • the weight ratio of polystyrene to the styrene/butadiene block copolymer resin is desirably from 95:5 to 20:80. If the proportion of the styrene/butadiene block copolymer resin is below the lower limit, the final sheet has low tear strength. If the proportion of the styrene/butadiene block copolymer resin is higher than the upper limit, the sheet has a low tensile modulus and lacks high stiffness inherent to a styrene resin. Furthermore, when the biaxially stretched composite styrene resin sheet is wound in roll form, it sticks to itself (blocking phenomenon), and is whitened or broken undesirably.
  • each outside layer formed of the styrene resin mixture is 1 to 20% of the total thickness of the biaxially stretched composite styrene resin sheet.
  • the sheet has low tear strength. If it exceeds the upper limit, the sheet has a low tensile modulus and inferior rigidity.
  • the thicknesses of layers formed of the styrene resin mixture in the sheet are equal to each other.
  • the biaxially stretched composite styrene resin sheet of this invention may be prepared, for example, by (l) preparing a multilayer sheet by co-extrusion and biaxially stretching it, (2) forming sheets by melt-extrusion, bonding these sheets while they are still at a high temperature to form a multilayer sheet, and then biaxially stretching the multilayer sheet, or (3) separating preparing sheets, bonding these sheets to each other with an adhesive, and biaxially stretching the resulting multilayer sheet.
  • Biaxial stretching is preferably carried out by a generally known tenter method or an inflation method at a stretch ratio of from 2 to 4.
  • the total thickness of the biaxially stretched composite styrene resin sheet is 0.l to l.0 mm.
  • the resin sheet in accordance with this invention is biaxially stretched such that its orientation relaxation stress measured in accordance with ASTM D-l504 is 0.294 to 1.470 MPa (3 to l5 kg/cm2), preferably 0.392 to 0.980 MPa (4 to l0 kg/cm2). If its orientation relaxation stress excesses the above-specified upper limit, the sheet cannot be molded into products conforming to a mold. If the sheet has an orientation relaxation stress below the above-specified lower limit, cracking occurs undesirably at the time of trimming.
  • the biaxially stretched composite styrene resin sheet of this invention has the following characteristics, it is useful for producing light-weight containers for holding foods and thus has very high industrial utility.
  • Polystyrene (DIC STYRENE CR-5600, a tradename for a product of Dainippon Ink and Chemicals, Inc.) and styrene/butadiene block copolymer resin (K RESIN KR-05, a tradename for a product of Phillips Petroleum International) were mixed by a tumbler in a weight ratio of 60:40 (Comparative Example l), 40:60 (Comparative Example 2) and 20:80 (Comparative Example 3).
  • the mixture was kneaded in an extruder equipped with a full-flight type screw having a diameter of 50 mm and formed into unstretched mixed sheets having a thickness of 0.l mm.
  • polystyrene (DIC STYRENE CR-5600, tradename) was melt-extruded from an extruder to form an unstretched sheet. While the sheets are at a high temperature, the unstretched mixed sheets were bonded to both surfaces of the unstretched sheet under 0.3 MPa (3 kg/cm2) to form a multilayer sheet. The thickness of the polystyrene sheet as a central layer was adjusted to 0.8 mm, and the entire thickness of the multilayer sheet, to l.0 mm.
  • the multilayer sheet was stretched at l30°C successively in the longitudinal direction (i.e., machine direction, MD) and the cross direction (CD) at a stretch ratio of 3 by a biaxial stretching device to obtain a biaxially stretched composite styrene resin sheet having a thickness of 110 ⁇ m.
  • the thickness of each of the outside layers of the stretched sheet was 11 ⁇ m, and the thickness of its central layer was 88 ⁇ m.
  • the tear strength of each of the three biaxially stretched composite styrene resin sheets was measured by a tensile tester ("Tensilon UTM-4-1000" made by Toyo Baldwin) at a pulling speed of 200 mm/min in accordance with JIS K6772.
  • the tensile modulus of the sheet was also measured at a pulling speed of 10 mm/min. in accordance with JIS K6872.
  • Table 1 Comparative Example Direction Tear strength (g) Tensile modulus (x 104 kg/cm2) MPa 1 MD 24.0 2550 (2.60) CD 28.0 2530 (2.58) 2 MD 27.5 2530 (2.58) CD 30.7 2500 (2.55) 3 MD 38.0 2450 (2.50) CD 43.5 2430 (2.48)
  • Polystyrene (DIC STYRENE CR-5600) and styrene/butadiene block copolymer resin (K RESIN KR-05) were mixed in a weight ratio of 92:8 (Comparative Example 4), 88:12 (Comparative Example 5) and 84:16 (Comparative Example 6).
  • the mixture was formed into an unstretched mixed sheet having a thickness of 1.0 mm by an extruder.
  • the mixed sheet was stretched at 130°C in the machine and cross directions at a stretch ratio of 3 by a biaxial stretching device to obtain a biaxially stretched polymer blend sheet containing the styrene/butadiene block copolymer resin in the same amount as in each of the biaxially stretched composite styrene resin sheets of Examples 1 to 3.
  • Tables 1 and 2 demonstrate that when the sheets containing the same amount of the styrene/butadiene block copolymer are compared, the biaxially stretched composite styrene resin sheets of Comparative Examples 1 to 3 have much higher tear strength than the biaxially stretched polymer blend sheets of Comparative Examples 4 to 6, and have high tensile moduli and high stiffness.
  • Polystyrene (DIC STYRENE CR-5600) and styrene/butadiene block copolymer (K RESIN KR-05) were mixed by a tumbler in a weight ratio of 80:20 (Example 1), 40:60 (Example 2) and 20:80 (Example 3).
  • unstretched co-extruded multilayer sheets each composed of a styrene resin mixture layer (0.067 mm)/a polystyrene layer (0.4 mm)/a styrene resin mixture layer (0.067 mm)/a polystyrene layer (0.4 mm)/a styrene mixture layer (0.067 mm) were formed by means of two extruders equipped with a full-flight type screw, feed block and a coat hanger die.
  • Each of the unstretched co-extruded multilayer sheets were successively stretched at 130°C in the machine and cross directions at a stretch ratio of 3 by means of a biaxially stretched device to give a biaxially stretched composite styrene resin sheet having a thickness of 110 ⁇ m.
  • the outside layers and the central layer each had a thickness of 7 ⁇ m, and the intermediate layers each had a thickness of 44 ⁇ m.
  • Polystyrene (DIC STYRENE CR-5600) and styrene/butadiene block copolymer resin (K RESIN KR-05) were mixed in a weight ratio of 94:6 (Comparative Example 7), 88:12 (Comparative Example 8) and 84:16 (Comparative Example 9).
  • the mixture was formed into an unstretched mixed sheet having a thickness of 1.0 mm by an extruder.
  • the mixed sheet was stretched at 130°C in the machine and cross directions at a stretch ratio of 3 by a biaxial stretching device to obtain a biaxially stretched polymer blend sheet containing the styrene/butadiene block copolymer resin in the same amount as in each of the biaxially stretched composite styrene resin sheets of Examples 1 to 3.
  • Polystyrene (DIC STYRENE CR-5600) and styrene/butadiene block copolymer resin (K RESIN KR-05) were mixed in a weight ratio of 94:6 (Comparative Example 10), 82:18 (Comparative Example 11) and 76:24 (Comparative Example 12).
  • the mixture was formed into an unstretched mixed sheet having a thickness of 1.0 mm by an extruder.
  • the mixed sheet was stretched at 130°C in the machine and cross directions at a stretch ratio of 3 by a biaxial stretching device to obtain a biaxially stretched polymer blend sheet containing the styrene/butadiene block copolymer resin in the same amount as in each of the biaxially stretched composite styrene resin sheets of Examples 4 to 6.
  • unstretched co-extruded multilayer sheets having a thickness of 1.0 mm composed of a styrene resin mixture/ polystyrene/styrene resin mixture/polystyrene/styrene resin mixture/polystyrene/styrene resin mixture and a layer thickness ratio of 5/26.7/5/26.7/5/26.7/5 were prepared by using two extruders having a screw diameter of 50 mm and equipped with a full-flight type screw, a feed block and a coat hanger die.
  • the multilayer sheets were then each stretched at 130°C in the machine and cross directions at a stretch ratio of 3 by means of a biaxial stretching device to obtain 110 ⁇ m-thick biaxially stretched composite styrene resin sheets.
  • each of the styrene resin mixture layers bad a thickness of 6 ⁇ m
  • each of the polystyrene layers had a thickness of 29 ⁇ m.
  • Polystyrene (DIC STYRENE CR-5600) and styrene/butadiene block copolymer resin (K RESIN KR-05) were mixed in a weight ratio of 96:4 (Comparative Example 13), 88:12 (Comparative Example 14) and 84:16 (Comparative Example 15).
  • the mixture was formed into an unstretched mixed sheet having a thickness of 1.0 mm by an extruder.
  • the mixed sheet was stretched at 130°C in the machine and cross directions at a stretch ratio of 3 by a biaxial stretching device to obtain a biaxially stretched polymer blend sheet containing the styrene/butadiene block copolymer resin in the same amount as in each of the biaxially stretched composite styrene resin sheets of Examples 7 to 9.
  • Unstretched co-extruded multilayer sheets composed of a styrene resin mixture/polystyrene/styrene resin mixture/polystyrene/styrene resin mixture/polystyrene/styrene resin mixture and having a layer thickness ratio of 2.5/30/2.5/30/2.5/30/2.5 (Example 10), 7.5/23.3/7.5/23.3/7.5/23.3/7.5 (Example 11), and 10/20/10/20/10/20/10 (Example 12) were prepared from a mixture of 40 parts by weight of polystyrene (DIC STYRENE CR-5600) and 60 parts by weight of stryrene/butadiene blocked copolymer resin (K RESIN KR-05) and polystyrene (DIC STYRENE CR-5600). Then, the sheets were each stretched at 130°C in the machine and cross directions at a stretch ratio of 3 to obtain biaxially stretched composite st
  • Polystyrene (DIC STYRENE CR-5600) and styrene/butadiene block copolymer resin (K RESIN KR-05) were mixed in a weight ratio of 94:6 (Comparative Example 16), 82:18 (Comparative Example 17) and 76:24 (Comparative Example 18).
  • the mixture was formed into an unstretched mixed sheet having a thickness of 1.0 mm by an extruder.
  • the mixed sheet was stretched at 130°C in the machine and cross directions at a stretch ratio of 3 by a biaxial stretching device to obtain a biaxially stretched polymer blend sheet containing the styrene/butadiene block copolymer resin in the same amount as in each of the biaxially stretched composite styrene resin sheets of Examples 10 to 12.

Landscapes

  • Laminated Bodies (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Claims (5)

  1. Feuille étirée biaxialement de structure multicouche, comprenant au moins deux couches de polystyrène et au moins trois couches d'un mélange de polystyrène et de résine de copolymère séquencé styrène/butadiène, dans laquelle les deux couches externes sont formées dudit mélange et les couches de polystyrène et du mélange de résine styrénique alternent dans la structure, l'épaisseur de chacune des couches externes valant 1 à 20% de l'épaisseur totale de ladite feuille, et la feuille entière étant étirée biaxialement.
  2. Feuille selon la revendication 1, qui posséde une structure à cinq couches comprenant une couche centrale, des couches intermédiaires sur les deux surfaces de la couche centrale, et lesdites couches externes formées à l'extérieur des couches intermédiaires, dans laquelle les couches intermédiaires sont formées de polystyrène et la couche centrale est formée dudit mélange.
  3. Feuille selon la revendication 1, qui posséde une structure à sept couches comprenant une couche centrale, des premières couches intermédiaires sur les deux surfaces de la couche centrale, des secondes couches intermédiaires à l'extérieur des premières couches intermédiaires, et lesdites couches externes formées à l'extérieur des secondes couches intermédiaires, dans laquelle la couche centrale et les secondes couches intermédiaires sont formées de polystyrène et les premières couches intermédiaires sont formées dudit mélange.
  4. Feuille selon l'une quelconque des revendications 1 à 3, dans laquelle le rapport pondéral du polystyrène à la résine de copolymère séquencé styrène/butadiène dans ledit mélange est compris entre 95:5 et 20:80.
  5. Récipients fabriqués à partir d'une feuille selon l'une quelconque des revendications précédentes.
EP87305547A 1986-06-23 1987-06-22 Feuille composite étirée biaxialement, en résine de styrène Expired - Lifetime EP0251636B1 (fr)

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
JP14651486 1986-06-23
JP146514/86 1986-06-23
JP25705086 1986-10-30
JP257050/86 1986-10-30
JP260455/86 1986-10-31
JP26045586 1986-10-31

Publications (3)

Publication Number Publication Date
EP0251636A2 EP0251636A2 (fr) 1988-01-07
EP0251636A3 EP0251636A3 (en) 1988-11-02
EP0251636B1 true EP0251636B1 (fr) 1992-03-25

Family

ID=27319199

Family Applications (1)

Application Number Title Priority Date Filing Date
EP87305547A Expired - Lifetime EP0251636B1 (fr) 1986-06-23 1987-06-22 Feuille composite étirée biaxialement, en résine de styrène

Country Status (4)

Country Link
US (1) US4835041A (fr)
EP (1) EP0251636B1 (fr)
JP (1) JP2570297B2 (fr)
DE (1) DE3777699D1 (fr)

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5004649A (en) * 1988-04-13 1991-04-02 Idemitsu Kosan Co., Ltd. Resin laminates and a process for production thereof
JPH02185438A (ja) * 1989-01-13 1990-07-19 Asahi Chem Ind Co Ltd スチレン系樹脂二軸延伸多層シート
JP2564257B2 (ja) * 1990-01-31 1996-12-18 出光石油化学株式会社 スチレン系樹脂シート
AT397386B (de) 1992-02-24 1994-03-25 Klepsch Liliana Ablösbare heisssiegelfähige folie
IT1266781B1 (it) * 1993-11-08 1997-01-21 Grace W R & Co Pellicole multistrato orientate biassialmente e termoretraibili, procedimento per produrle e loro uso per confezionare prodotti
DE4441006C2 (de) * 1994-11-17 1997-07-31 Brueckner Maschbau Biaxial orientierte heißsiegelbare Polystyrol-Verbundfolie, Verfahren zu ihrer Herstellung sowie ihre Verwendung
US5756577A (en) * 1995-03-27 1998-05-26 Grupo Cydsa, S.A. De C.V. Styrene butadiene copolymer and polyolefin resins based shrink films
US6905568B2 (en) * 1998-12-30 2005-06-14 Phillips Petroleum Company Process for minimizing haze of extruded clear blends containing styrene/butadiene polymer and product thereof
JP4700776B2 (ja) * 1999-07-27 2011-06-15 ダイセル化学工業株式会社 合成樹脂シート

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5526611B2 (fr) * 1973-05-09 1980-07-15
CA1069814A (fr) * 1975-10-22 1980-01-15 Ernest J. Buckler Stratifies renfermant du polystyrene injecte
JPS5920557B2 (ja) * 1978-06-29 1984-05-14 電気化学工業株式会社 包装体
JPS5638254A (en) * 1979-09-07 1981-04-13 Idemitsu Petrochemical Co Multilayer structure
JPS58196239A (ja) * 1982-05-11 1983-11-15 Sekisui Plastics Co Ltd 二次成形に適したポリスチレン系発泡シ−ト
JPS6032658A (ja) * 1983-08-02 1985-02-19 旭化成株式会社 ポリスチレンシ−ト成形材料

Also Published As

Publication number Publication date
JPS63227338A (ja) 1988-09-21
EP0251636A3 (en) 1988-11-02
DE3777699D1 (de) 1992-04-30
US4835041A (en) 1989-05-30
EP0251636A2 (fr) 1988-01-07
JP2570297B2 (ja) 1997-01-08

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